Antimicrobial solid and method of making same

ABSTRACT

A solid material adapted to kill bacteria in planktonic, spore and biofilm states is lethal toward a wide spectrum of gram positive and gram negative bacteria as well as other microbes. The solid material includes a significant amount of one or more surfactants entrained in a crosslinked polymeric network.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.14/485,748, filed 14 Sep. 2014 and issued as U.S. Pat. No. 10,045,527 on14 Aug. 2018, which is a continuation of U.S. application Ser. No.13/468,767, filed 10 May 2012 and presently pending, which claims thebenefit of U.S. provisional appl. No. 61/484,558 filed 10 May 2011, theentire disclosures of each being incorporated herein by reference.

BACKGROUND INFORMATION

Bacteria is found virtually everywhere and is responsible for asignificant amount of disease and infection. Killing and/or eliminatingthese microorganisms is desirable to reduce exposure and risk ofdisease.

Bacteria in many environments are present in high concentrations andhave developed self preservation mechanisms and, therefore, areextremely difficult to remove and/or eradicate. They can exist inplanktonic, spore and biofilm forms.

In a biofilm, bacteria interact with surfaces and form surface colonieswhich adhere to a surface and continue to grow. The bacteria produceexopolysaccharide (EPS) and/or extracellularpolysaccharide (ECPS)macromolecules that keep them attached to the surface and form aprotective barrier effective against many forms of attack. Protectionmost likely can be attributed to the small diameter of the flow channelsin the matrix, which restricts the size of molecules that can transportto the underlying bacteria, and consumption of biocides throughinteractions with portions of the EPS/ECPS macromolecular matrix.

Bacteria often form spores, which provide additional resistance toeradication efforts. In this form, the bacteria create a hard,non-permeable protein/polysaccharide shell around themselves whichprevents attack by materials that are harmful to the bacteria.

Additionally, bacteria in biofilm- or spore forms are down-regulated(sessile) and not actively dividing. This makes them resistant to attackby a large group of antibiotics and antimicrobials, which attack thebacteria during the active parts of their lifecycle, e.g., celldivision.

Due to the protection afforded by a macromolecular matrix (biofilm) orshell (spore) and their down-regulated state, bacteria in biofilm- andspore states are very difficult to treat. The types of biocides andantimicrobials effective in treating bacteria in this form are stronglyacidic, oxidizing, and toxic, often involving halogen atoms, oxygenatoms, or both. Common examples include concentrated bleach, phenolics,strong mineral acids (e.g., HCl), hydrogen peroxide and the like.Commonly, large dosages of such chemicals are allowed to contact thebiofilm or spore for extended amounts of time (up to 24 hours in somecircumstances), which makes them impractical for many applications.

Recently developed formulations intended for use in connection withcompromised animal/human tissue can solvate a biofilm matrix so thatstill-living bacteria can be rinsed or otherwise removed from infectedtissue; the concentrations of active ingredients in these formulationsare too low to effectively kill the bacteria, thus making them illsuited for use as disinfecting agents. More recently, solutions that candisrupt the macromolecular matrix, or bypass and/or disable the defensesinherent in these matrices, allowing lethal doses of anti-microbialingredients in the solutions to access and kill the bacteria in theirbiofilm and sessile states have been described; unlike theaforementioned formulations, these solutions can be used asdisinfectants.

Most water filtration is accomplished using filters made of materialssuch as paper, fiber, and synthetic fibers. Unclean, bacteria-ladenwater is passed through a membrane having a controlled pore size,typically on the order of ˜0.20 to ˜0.45 μm. These membranes areeffective at keeping bacteria from passing through them into a cleanwater reservoir, but they do not weaken, disable or kill the bacteria.This latter characteristics make such membranes susceptible to bacterialgrowth, thereby increasing the risks of contamination with biofilms andspore-forming bacteria and reduced flow rates due to clogging.

Silver-loaded ceramic filters use the antimicrobial properties of silverto kill bacteria as they pass through a porous ceramic substrate. Toachieve high efficacy, flow rates must be kept low. Further, thesefilters have a high propensity for clogging. Finally, silver ions arenot particularly efficacious in debilitating and killing bacteria inbiofilm- and spore forms.

Devices and articles can be provided with coatings that includeantimicrobials such as cationic compounds (e.g., quaternary ammoniacompounds), silver and copper compounds, and peptides. These coatingsare limited in their efficacy against resistant forms of bacteria andhave very thin regions of effective antimicrobial effect. These types ofcoatings are generally designed to prevent surface attachment ofbacteria rather than to disinfect.

Certain eluting devices and articles are designed to slowly releaseantibacterial compounds when exposed to moisture. These solids typicallybeen impregnated by antimicrobial agents which, over time, work theirway to the surface and are released. The concentrations of solutionseluted from these devices and articles, as well as the efficacy of theemployed antimicrobial agents against resistant forms of microbes, arelow. The utility of such devices and articles is further reduced insituations where a liquid is to pass through the device due to morerapid depletion of the antimicrobial agent(s).

A solid material capable of preventing bacterial growth, and preferablykilling bacteria coming into contact with or close proximity to thesolid material, remains desirable. Such a solid preferably can be usefulin a variety of forms including, but not limited to, filters, elutingdevices, and coatings.

SUMMARY

Liquid compositions effective for disinfection purposes are described inU.S. Pat. Publ. No. 2010/0086576 A1. Those compositions display bothmoderately high tonicity (i.e., large amounts of osmotically activesolutes) and relatively low pH (about 4≤pH≤6) which work withsurfactants to induce membrane leakage in bacteria, leading to celllysis. The composition acts at least in part to interrupt or break ioniccrosslinks in the macromolecular matrix of a biofilm, facilitating thepassage of solutes and surfactant through the matrix to bacteriaentrained therein and/or protected thereby. In addition to being lethaltoward a wide spectrum of gram positive and gram negative bacteria,these liquid compositions also exhibit lethality toward other microbessuch as viruses, fungi, molds, and yeasts.

However, some end-use applications are not conducive to the relativelyhigh concentrations that provide the liquid compositions with theirefficacy. These include, but are not limited to, applications where ahigh concentration of free (unbound) species of these ingredients isunacceptable, applications where an extremely large volume of liquidneeds to be disinfected, and applications where such ingredients will beconsumed.

The solid materials of the present invention are designed and intendedto achieve, in a non-liquid form, a set of characteristics similar tothose displayed by the aforementioned liquid compositions: high tonicityand surfactant availability.

These solid materials, adapted to kill bacteria in planktonic, spore andbiofilm states, include a crosslinked version of a water solublepolyelectrolyte and entrained surfactant. This combination of componentspermits the local chemistry within the solid material and in itsimmediate vicinity, when in use in an aqueous environment, to mimic thatof the previously described liquid disinfecting composition: hightonicity and high surfactant concentration. In at least someembodiments, the solid material includes no biocidal additives,particularly active antimicrobial agents.

In certain aspects, the solid material can be prepared by crosslinking aliquid or flowable polyelectrolyte in the presence of the surfactant(s).

Also provided are methods of using the foregoing composition. When aliquid is passed through or in proximity to the solid material, anybacteria or other microorganism is exposed to the local chemistryconditions discussed above: high tonicity, relatively low pH, andavailable surfactant, a combination that can induce membrane leakage inbacteria leading to cell lysis. These characteristics permit the solidmaterial to be very effective at bypassing and disabling bacterialbiofilm and spore defenses, allowing the solid material to kill bacteriain any of its several states.

The solid material can be used to disinfect liquids, in either filter orinsert form, and as surface coating that prevents bacterialcontamination by killing any bacteria that come into contact therewith.That it can perform these tasks while losing or transmitting very littleof its chemical components into the environment being treated is bothsurprising and advantageous. Further, any chemical components that doenter the environment are relatively benign.

To assist in understanding the following description of variousembodiments, certain definitions are provided immediately below. Theseare intended to apply throughout unless the surrounding text explicitlyindicates a contrary intention:

-   -   “microbe” means any type of microorganism including, but not        limited to, bacteria, viruses, fungi, viroids, prions, and the        like;    -   “antimicrobial agent” means a substance having the ability to        cause greater than a 90% (1 log) reduction in the number of one        or more of microbes;    -   “active antimicrobial agent” means an antimicrobial agent that        is effective against a microbe only or primarily during the        active parts of its lifecycle, e.g., cell division;    -   “biofilm” means a community of microbes, particularly bacteria        and fungi, attached to a surface with the community members        being contained in and/or protected by a self-generated        macromolecular matrix;    -   “residence time” means the amount of time that an antimicrobial        agent is allowed to contact a bacterial biofilm;    -   “biocompatible” means presenting no significant, long-term        deleterious effects on or in a mammalian species;    -   “biodegradation” means transformation, via enzymatic, chemical        or physical in vivo processes, of a chemical into smaller        chemical species;    -   “polyelectrolyte” means a polymer with multiple mer that include        an electrolyte group capable of dissociation in water;    -   “strong polyelectrolyte” is a polyelectrolyte whose electrolyte        groups completely dissociate in water at 3≤pH≤9;    -   “weak polyelectrolyte” is a polyelectrolyte having a        dissociation constant of from ˜2 to ˜10, i.e., partially        dissociated at a pH in the range where a strong        polyelectrolyte's groups are completely dissociated; and    -   “polyampholyte” is a polyelectrolyte with some mer including        cationic electrolyte groups and other mer including anionic        electrolyte groups.

Hereinthroughout, pH values are those which can be obtained from any ofa variety of potentiometric techniques employing a properly calibratedelectrode.

The relevant portions of any specifically referenced patent and/orpublished patent application are incorporated herein by reference.

DETAILED DESCRIPTION

The antimicrobial solid material can contain as few as two components: acrosslinked polymer network and at least one entrained surfactant, eachof which generally is considered to be biocompatible. Certainembodiments of the composition employ no active biocides. In these andother embodiments, the identity of the polymers and surfactants, as wellas the concentrations in which each is discharged from the solidmaterial, can be such that recognized toxicity limits are not exceededduring normal use.

The solid material is lethal to planktonic and bacterial cells with highefficacy, is not readily consumed, provides a significant amount ofsurface area for microbial interactions, and does not create toxicity insolutions being treated. The solid material is not particularly solublein water under most conditions (e.g., moderate temperatures and soluteconcentrations), but the polyelectrolyte chains are at least hydrophilicand, where the solid material is to be used in a setting where it mightnot be immersed in an aqueous medium, preferably hygroscopic, therebypermitting the solid material to swell somewhat when in the presence ofmoisture, particularly water.

The solid material of the present invention requires some level of wateror humidity to function appropriately. This can be determined or definedin a variety of ways. The polyelectrolytes must be capable of localizedliquid charge interaction (meaning at least two water molecules arecontacting or very near an electrolyte group); alternatively, sufficientwater must be present to activate the charge of the electrolyte; and/orsufficient water to permit bacterial growth. As non-limiting examples,gaseous or liquid water can be applied directly to the solid material orcan result from other, indirect means, e.g., water vapor contained inbreath or ambient air, condensates, etc.

Because the antimicrobial material is solid, it does not itself have atrue pH; in use, however, the local pH of any aqueous composition inwhich it is deployed preferably is lower than ˜7 to ensure properantimicrobial activity. Reduced pH values (e.g., less than ˜6.5, ˜6.0,˜5.5, ˜5.0, ˜4.5 and even ˜4.0) generally are believed to correlate withincreases in efficacy of the solid material, although this effect mightnot be linear, i.e., the enhancement in efficacy may be asymptotic pasta certain hydronium ion concentration. Without wishing to be bound bytheory, acidic protons (i.e., hydronium ions) might be involved inbreaking ionic crosslinks in the macromolecular matrix of a biofilm.

In addition to more strongly acidic local environments, high localosmolarity conditions also are believed to increase efficacy.Accordingly, larger concentrations of poly-electrolytes, largerconcentrations of surfactant, surfactants with shorter chain lengths(e.g., no more than C₁₀, typically no more than C₈, commonly no morethan C₆), and surfactants with smaller side groups around the polargroup each are more desirable.

The lethality of the surfactant component(s) is increased and/orenhanced when the solid material can provide to the local environment inwhich it is deployed at least moderate effective solute concentrations(tonicity). (In biological applications, a 0.9% (by wt.) salinesolution, which is ˜0.3 Osm/L, typically is considered to be havemoderate tonicity, while a 3% (by wt.) saline solution, which is ˜0.9Osm/L, generally is considered to be hypertonic.) Without wishing to bebound by theory, higher tonicities may exert higher osmotic pressure tothe bacterial cell wall, which increases its susceptibility tointerruption by surfactant. Local osmolarity (tonicity) generallyincreases in proportion to the number and type of electrolytes presentin the polymeric network. (By local osmolarity is meant that of a liquidcontained in the solid material. While this might vary from place toplace throughout the article, preference is given to those solidmaterials capable of providing high local osmolarities throughout.)

The polyelectrolyte(s) that form the bulk of the solid materialpreferably are at least somewhat water soluble but also essentiallywater insoluble after being crosslinked. A partial list ofpolyelectrolytes having this combination of characteristics included,but are not limited to, strong polyelectrolytes such as polysodiumstyrene sulfonate and weak poly-electrolytes such as polyacrylic acid,pectin, carrageenan, any of a variety of alginates,poly-vinylpyrrolidone, carboxymethylchitosan, andcarboxymethylcellulose. Included in potentially useful polyamphyolytesare amino acids and betaine-type cross-linked networks; examples wouldbe hydrogels based on sodium acrylate andtrimethylmethacryloyloxyethylammonium iodide,2-hydroxyethylmethacrylate, or 1-vinyl-3(3-sulfopropyl)imidazoliumbetaine. Those polymeric materials having electrolyte groups thatcompletely (or nearly completely) dissociate in water and/or providerelatively low local pH values are desired for efficacy are preferred.

Also preferred are those polyelectrolytes having a high density of merwith electrolyte-containing side groups. Without wishing to be bound bytheory, the large number of acidic or polar side groups on thepolyelectrolyte are believed to function equivalently to the hightonicity solution of the previously described liquid composition.

Several crosslinking mechanisms including but not limited to chemical,high temperature self-crosslinking (i.e., dehydrothermal crosslinking),and irradiation (e.g., e-beam or gamma rays) can be employed. Theordinarily skilled artisan can discern and select an appropriatecrosslinking mechanism once a polyelectrolyte is selected.

Another option is to create crosslinks during the polymerization processitself, such as by condensing adjacent sulfonic acid groups to yieldsulfonyl crosslinks.

Independent of crosslinking method, the solid material can be formed bycross-linking polymers (or polymerizable monomers) in an aqueoussolution contained in a heat conductive mold, followed by rapid freezingand subsequent lyophilizing. The resulting sponge-like materialgenerally takes the shape of the mold in which it was formed. Apotential advantage of this process is that it can provide a ready meansfor removing any hazardous or undesirable precursor chemicals used inthe polymerization and/or crosslinking steps. Solids resulting from thistype of process often have a spongy appearance, with relatively largepores connected by tortuous paths. Often, pores less than ˜0.22 μm, lessthan ˜0.45 μm, less than ˜0.80 μm, and less than ˜0.85 μm are desirable(based on the diameters of endotoxins, bacteria, and spores); for theseand other applications, a solid material with at least some larger pores(e.g., less than ˜1, 2, 5, 10, 50, or 100 μm) can be used.

The crosslink density in the solid material plays an important role,specifically, those solid materials with higher crosslink densities tendto maintain higher surfactant concentrations for a longer period of timedue to, presumably, longer mean free paths in the polymeric network.

The solid material contains a sufficient amount of surfactant tointerrupt or rupture cell walls of bacteria contacting or coming intothe vicinity of the solid material. This amount can vary widely based ona variety of factors including, for example, whether a biofilm alreadyexists in the area to be treated (and whether that biofilm isentrenched, a factor which relates to the type of proteins and mass ofthe macromolecular matrix), the species of bacteria, whether more thanone type of bacteria is present, the solubility of the surfactant(s) inthe local environment, and the like. The surfactant component(s)generally constitute as low as ˜0.03% and as high as ˜10%, ˜15% or even˜17.5% (all by wt.) of the solid material.

Essentially any material having surface active properties in water canbe employed, although those that bear some type of ionic charge areexpected to have enhanced antimicrobial efficacy because such charges,when brought into contact with a bacteria, are believed to lead to moreeffective cell membrane disruption and, ultimately, to cell leakage andlysis. This type of antimicrobial process can kill even sessile bacteriabecause it does not involve or entail disruption of a cellular process.Cationic surfactants are most desirable followed by, in order,zwitterionic, anionic and non-ionic.

Potentially useful anionic surfactants include, but are not limited to,sodium chenodeoxycholate, N-lauroylsarcosine sodium salt, lithiumdodecyl sulfate, 1-octane-sulfonic acid sodium salt, sodium cholatehydrate, sodium deoxycholate, sodium dodecyl sulfate, sodiumglycodeoxycholate, sodium lauryl sulfate, and the alkyl phosphates setforth in U.S. Pat. No. 6,610,314. Potentially useful cationicsurfactants include, but are not limited to, hexadecylpyridiniumchloride monohydrate and hexadecyltrimethyl-ammonium bromide, with thelatter being a preferred material. Potentially useful non-ionicsurfactants include, but are not limited to, polyoxyethyleneglycoldodecyl ether, N-decanoyl-N-methylglucamine, digitonin, n-dodecylB-D-maltoside, octyl B-D-gluco-pyranoside, octylphenol ethoxylate,polyoxyethylene (8) isooctyl phenyl ether, polyoxy-ethylene sorbitanmonolaurate, and polyoxyethylene (20) sorbitan monooleate. Potentiallyuseful zwitterionic surfactants include, but are not limited to,3-[(3-cholamidopropyl) dimethylammonio]-2-hydroxy-l-propane sulfonate,3-[(3-cholamidopropyl) dimethyl-ammonio]-1-propane sulfonate,3-(decyldimethylammonio) propanesulfonate inner salt, andN-dodecyl-N,N-dimethyl-3-ammonio-l-propanesulfonate. For otherpotentially useful materials, the interested reader is directed to anyof a variety of other sources including, for example, U.S. Pat. Nos.4,107,328 and 6,953,772 as well as U.S. Pat. Publ. No. 2007/0264310,including quaternary amine compounds of the general formula

where R, R′, R″ and R′″ are each a C₁-C₂₄ alkyl, aryl or aralkyl groupthat can optionally contain one or more P, 0, S or N heteroatoms, and Xis F, Cl, Br, I or an alkyl sulfate.

The surfactant preferably is present in the polymer network at the timethat cross-linking occurs (or the time of polymerization in the case ofthe type of simultaneous polymerization and condensation discussedabove). If it is not, a crosslinked polymer article or film must bepost-treated to ensure proper entrainment of the surfactant. A possiblemethod for accomplishing this is immersion of the article or film in anaqueous solution that contains one or more surfactants, followed byremoval of excess water via a drying (e.g., thermal or freeze) orevacuation process.

In certain embodiments, the surfactant(s) can be the only antimicrobialagents in the composition, specifically, the composition can be free ofactive antimicrobial agents.

In addition to the surfactant(s), one or more ionic compounds (salts)can be incorporated into the solid material so as to enhance its abilityto create localized regions of high tonicity.

Regardless of how achieved, the local tonicity around the solid materialis at least moderately high, with an osmolarity of at least about 0.1Osm/L being preferred for most applications. Solid materials that createlocal osmolarities greater than about 0.1 Osm/L will have enhancedbactericidal activity; increases in the osmotic pressure applied to thebacteria enhance antimicrobial efficacy.

A variety of additives and adjuvants can be included to make a solidmaterial more amenable for use in a particular end-use applicationwithout negatively affecting its efficacy in a substantial manner.Examples include, but are not limited to, emollients, fungicides,fragrances, pigments, dyes, abrasives, bleaching agents, preservatives(e.g., antioxidants) and the like. Depending on the identity and natureof a particular additive, it can be introduced at any of a variety oftimes during production of the solid material.

The solid material does not require inclusion of an active antimicrobialagent for efficacy, but such materials can be included in certainembodiments. For example, one or more of bleach, any of a variety ofphenols, aldehydes, etc., can be added.

As previously stated, bacteria present in a biofilm derive some inherentprotection offered by the EPS/ECPS macromolecular matrix. Withoutwishing to be bound by theory, the high tonicity and slightly acidicnature of the solid material (as well as the region immediatelysurrounding it when it is in use) are believed to interfere with andbreak the ionic crosslinks in the macromolecular matrix of any biofilmpassing near or through the material, thus permitting better access tothe previously protected bacteria. Additionally, the high tonicityprovided in and around the solid material means that an abundance ofions are available, even though some are consumed in the EPS. These ionscan assist in killing the bacteria while they remain in the biofilm andafter they are freed therefrom, perhaps by making the bacterial cellwalls susceptible to being ruptured by the surfactant component(s).

Thus, the solid material that includes one or more surfactants entrainedin a polymer network possesses a combination of characteristics andattributes that allow it to be a highly effective yet non-toxicantimicrobial:

-   -   1) a capability to provide an aqueous liquid contacting it a        local pH (in and/or very near it) of less than 7, preferably        less than 6;    -   2) the polymeric network is hydrophilic (and, where the solid        material is intended for use at least some of the time in a        non-immersed state, perhaps even hygroscopic);    -   3) a capability to provide an aqueous liquid contacting it an        effective local solution osmolarity (in and/or very near the        solid material) of at least ˜0.1 Osm/L;    -   4) a sufficient concentration of one or more surfactants to        rupture cell walls of bacteria contacting or coming near to the        solid material; and    -   5) a crosslink density of the polymeric network is great enough        to greatly slow the rate of surfactant loss from the material.

This solid material is actively antimicrobial, has greater antimicrobialefficacy against bacteria in resistant forms, is not rapidly consumed,and does not create toxicity in the medium being treated.

The solid material can take any of a variety of intermediate and finalshapes or forms including, but are not limited to, a spongy solid thatis permeable to vapor and or liquids; a molded, extruded or depositedsheet; and an extruded fiber or thread. Once in a particular shape, thematerial then can be further processed or manipulated so as to provide adesired shape, e.g., a sheet good can be rolled or folded so as toprovide a membrane of a particular geometry. Thus whether the materialis used in its manufactured form or it is post processed by thermalforming, mechanical shaping, lamination, granulation, pulverization,etc., it is considered to be within the present disclosure.

A single, non-limiting example of a potential use for a solidantimicrobial material is as a filter (or part of a filtration device)to be placed in the flow path of a vapor or liquid passingthere-through, -over or -by. Such a material can be housed, sealed, oradhered in a variety of ways so as to permit fluid flow to be directedthrough, around, or over it.

A filter can be provided by making a spongy solid (via, for example, alyophilization process such as the one described above) with asurfactant trapped therein. Water can be passed through or past thespongy solid, which will work as a filter device, which is activelyantimicrobial and kills any bacteria passing through the element.

Such a filter can have high flow rates because of its activeantimicrobial nature and, therefore, can have larger pore sizes thancurrent sterile filters which rely on extremely small pores to preventpassage of bacteria through the filter. Larger pores also mean that sucha filter will be less susceptible to clogging, thus increasing itsviable lifecycle. Thus, the resulting filtration device has highbactericidal activity toward planktonic and bacterial cells, permitshigh fluid flow rates, is less susceptible to clogging, and producesdisinfected water which is non-toxic when ingested.

As an alternative to a spongy, amorphous mass, a much more structuredform, e.g., a fabric (woven or nonwoven) made from or incorporatingthreads provided from a solid antimicrobial material of the presentinvention, also can be employed for such filtration applications.

In addition to water filtration, other potential uses for solidmaterials of the present invention include, but are not limited to, airfilters, odor controlling articles (e.g., clothing such as socks, shoeinserts, etc.), pool water treatment articles, disinfecting wipes, minewaste pool barriers (to prevent acidic leakage due to bacterialactivity), bandages, humidifier wicking elements, layers in personalprotection articles such as diapers and feminine hygiene products, andthe like.

The solid material of the present invention also can be used as anantimicrobial surface coating or external surface layer for theprevention of bacterial contamination of the protected surface. In thismanner, the material will kill bacteria, in any form, coming intocontact with the surface of the material. Potential end use applicationsfor such coatings include, but are not limited to, cooler surfaces,refrigerator interiors, drip pans (e.g., refrigerators, dehumidifiers,etc.), food storage containers, tracheotomy tubes, external surfaces oftemporarily or permanently implanted medical devices, contact surfacesin medical equipment (e.g., fluid lines, fittings, joints, reservoirs,covers, etc.), reagent bottles, telephone and remote control surfaces(e.g., buttons), medical devices intended to contact more than onepatient (e.g., blood pressure cuffs, stethoscopes, wheelchairs, gurneys,etc.), plumbing fixtures, pipes and traps, recreational vehicle cisternsand tanks, shower walls and components, canteens, beverage dispensersand transfer lines, baby feeding equipment (e.g., bottles, nipples,etc.), pacifiers, teething rings, toys, playground and exerciseequipment, outdoor equipment (e.g., tents, boat covers, sleeping bags,etc.), and the like.

As is clear from the foregoing description, the solid material may takemany different physical forms and find use in a variety of devices. Itscomponents can be provided from a wide variety of materials, and itspolymer network can be crosslinked in a variety of ways. Thus, theordinarily skilled artisan understands that the functionality of thecomponents and not their specific identity or manner of processing isthat which is most important; the ever evolving fields of chemistry andpolymer science are anticipated to provide additional options not knownat the time of this writing that provide similar functionality. (By wayof non-limiting example, surfactants are described here as a keycomponent for providing bactericidal activity; however, newly developedcompounds that do not fit entirely within the definition of “surfactant”yet still possess the types of charged or polar side groups that providethe same functional mechanism are quite reasonably expected to be usefulin solid material.)

While various embodiments of the present invention have been provided,they are presented by way of example and not limitation. The followingclaims and their equivalents define the breadth and scope of theinventive methods and compositions, and the same are not to be limitedby or to any of the foregoing exemplary embodiments.

That which is claimed is:
 1. An article having at least one surfaceadapted to kill bacteria coming in contact therewith, said articlecomprising a substrate and, disposed on at least one surface of saidsubstrate, a solid antimicrobial coating that comprises (a) ahydrophilic network of crosslinked poly-vinylpyrrolidone and (b) one ormore cationic surfactants entrained in said polymer network, saidcoating being adapted to be effective when in contact with water.
 2. Thearticle of claim 1 wherein said substrate is a medical device intendedfor temporary implantation and wherein said surface is an externalsurface of said device.
 3. The article of claim 1 wherein said one ormore cationic surfactants constitute from 0.03 to 10 weight percent ofsaid solid antimicrobial coating.
 4. The article of claim 3 wherein saidone or more cationic surfactants comprises a quaternary ammonium halide.5. The article of claim 4 wherein said one or more cationic surfactantsis a quaternary ammonium halide.
 6. The article of claim 1 wherein saidone or more cationic surfactants comprises a quaternary ammonium halide.7. The article of claim 6 wherein said one or more cationic surfactantsis a quaternary amine compound.
 8. The article of claim 1 wherein saidsubstrate is a tracheotomy tube.
 9. The article of claim 1 wherein saidsubstrate is a contact surface of medical equipment.
 10. The article ofclaim 1 wherein said substrate is a patient contact surface of a medicaldevice selected from blood pressure cuffs, stethoscopes, wheelchairs andgurneys.
 11. The article of claim 1 wherein said coating furthercomprises one or more ionic compounds entrained in said polymer network.12. The article of claim 11 wherein said coating, when in contact withan aqueous medium, is capable of providing a local pH of less than 6.13. The article of claim 1 wherein said coating, when in contact with anaqueous medium, is capable of providing a local pH of less than
 6. 14.An article having at least one surface adapted to kill bacteria comingin contact therewith, said article comprising a medical device intendedfor temporary implantation and, disposed on an external surface of saiddevice, a solid antimicrobial coating adapted to be effective when incontact with water, said coating comprising (a) a hydrophilic network ofcrosslinked polyvinylpyrrolidone, (b) at least 0.03 weight percent of aquaternary ammonium halide surfactant entrained in said polymer network,and (c) one or more ionic compounds entrained in said polymer network,said coating, when in contact with an aqueous medium, being capable ofproviding a local pH of less than
 6. 15. The article of claim 14 whereinsaid substrate is a medical device intended for temporary implantationand wherein said surface is an external surface of said device.